Metal cleaning compositions and method and baths therefor



United States Patent O 3,322,573 METAL CLEANING COMPOITIONS AND METHOD AND BATHS THEREFOR Clarence Bremer, Rutherford, and Samuel S. Frey, Elizabeth, N.J., assignors t Oakite Products, Inc., New

York, N.Y., a corporation of New York No Drawing. Filed Jan. 19, 1965, Ser. No. 426,674

12 Claims. (Cl. 1341) This is a continuation-in-part of our co-pending application Ser. No. 672,862, filed July 19, 1957, now abancloned.

This invention is that of water-soluble alkaline compositions containing as their essential ingredients (i) at least one of the polyamines ethylene diamine, propylene diamine and diethylenetriamine, and '(ii) a soap made from reacting the recovered mixed fatty acids and tall oil (which mixed acids are described more fully below) with at least one of these polyamines, and in such a ratio as to leave an excess of the polyamine reactants (a) to serve as the aforesaid polyamine ingredient of the composition, and (b) to the extent of less than a mole of free polyamine per mole of soap ingredient and such that an aqueous solution prepared them dissolving in water from about two to about four ounces of this polyamineand-soap-containing composition by weight per gallon of resulting aqueous solution has a pH of from about 9 to about 11 .and can remove generally within about a few minutes, and often in under a minute, incrustations of buffing compounds from recesses as well as grooves on rigid articles, upon subjecting them immersed in said aqueous solution to the influence of waves of ultrasonic frequency of from about fifteen to about forty kilocycles per second.

The invention includes also such aqueous alkaline baths prepared by dissolving any of these water-soluble and alkaline polyamine and soap containing compositions in water in a concentration as above-noted whereby these baths are effective jointly with the ultrasonic waves for advantageously cleaning of adherent waterinsoluble dirt or soil incrustations, including those of bufling compounds, from deformations such as crevices, grooves and recesses on various kinds of rigid articles or metal products.

Another part of the invention is the method of ultrasonic Wave cleaning of such dirt or soil from metals by submerging these various articles or objects with such adherent dirt and incrustations in these aqueous alkaline baths and subjecting such soiled metal or other rigid articles or objects to the influence of waves of ultrasonic frequency transmitted within the indicated range through the aqueous alkaline cleaning bath.

Many metal parts or other fabricated products are frequently subjected to a finishing treatment to apply .a protective or decorative coating such as lacquering of electroplating before they are ready for sale. In practically all cases for such further treatment, the article or prod uct must have a clean and polished surface for the lacquer coating or electrodeposit or other coating to be reliably adherent. In preparing the articles or products for such coating, it is a common practice particularly with electrodeposits, for example, to subject them to bufling or polishing and with the use of the usual buffing compounds.

These procedures leave these objects dirtied and soiled with tough incrustations of the bufling compounds in their various surface deformations especially in crevices and other recessed and grooved areas. Such incrustations often are heavy and dense because of the pressures necessarily employed in the bufling and polishing, and ordinarily are removed with difficulty and at considerable expense and disadvantage. For example, the common organic solvents usually do not remove them completely or otherwise take much too much time and at necessarily increased cost.

The same occurs with ordinary detergents, soaps, and alkaline cleaners; and even various special formulated soap solutions require very high temperature often at or near that of boiling water. These various drastic conditions frequently cause corrosion and staining of the metal objects particularly With the sensitive metals, for example, non-ferrous metals and alloys such as zinc, brass, antimony-lead, and the like. Ultrasonic cleaning also was not available or applicable because the available transducer could not be used at the required temperatures that exceeded 150 to 160 F.

These various shortcomings and disadvantages are overcome by the method of the invention by the use of the compositions and baths constituting part of the invention.

Considered broadly, the water-soluble alkaline compositions of the invention comprise (i) a lower aliphatic straight chain polyamine having from two to four carbon atoms and selected from the polyamines ethylenediamine, propylenediamine and diethylenetriamine, and (ii) a soap of at least one of said aliphatic straight chain polyamines reacted with the recover mixed fatty acids of tall oil, with the latter and the polyamine reactant so proportioned to one another (a) to leave an excess of less than one mole of the polyamine per mole of the resulting soap, to serve as the above-noted polyarnine constituent of the composition, and (b) provide a pH from about nine to about eleven when the water-soluble alkaline composition of the invention is dissolved in water in an amount of from about two to about four ounces (by weight) per gallon of resulting aqueous solution.

The ultrasonic wave cleaning baths of the invention comprise any of the foregoing water-soluble alkaline compositions of the invention dissolved in water to a concentration of from about two to about four ounces (by weight) per gallon of aqueous alkaline bath solution.

Then the method of the invention comprises submerging soiled rigid objects or metal articles to be cleaned in an aqueous alkaline bath having a pH from about 9 to about 11 by containing dissolved therein from about two to about four ounces (by weight) of a composition of the invention per gallon of the bath, and subjecting the so submerged articles to the influence of waves of ultrasonic frequency (in the range of from about fifteen to forty kilocycles per second) transmitted to the articles through the aqueous alkaline cleaning bath, and advantageously at an elevated temperature below about 160 F. and preferably under about 150 F., and for a time suflicient for the article to be cleaned. That is usually from about one-half minute to about two and one-half minutes, and so far as presently noted for the most part under one minute.

It is highly advantageous not only as to actual operation but also economical to use as the soap constituent of the water-soluble alkaline compositions of the invention the soap prepared by reacting one or more of the polyamines ethylene diamine, propylene diamine, and dieth-ylenetriamine with the recovered mixed fatty acids from tall oil.

By recovered mixed fatty acids from tall oil as used herein is meant generically the mixed acids product obtained in the tall oil industry from tall oil, and therein called tall oil fatty acids. This product generally contains as by far its major portion, ordinarily exceeding eightyfive percent and more often being over ninety percent, the unsaturated fatty acids, namely, (a) oleic acid and (b) linoleic .acid, in roughly about equal parts and more often with the oleic acid in slight excess, with both of them generally amounting to between 3 eighty-five (85) and ninety-five (95) percent of all the acids, and (c) linolenic acid from none up to possibly about five percent of the product, together with saturated fatty acids usually under five (5%) percent, sometimes as little as two (2%) percent, and often between two (2) and three (3) percent, and also a small percentage substantially less than ten percent, most often not exceeding five (5 percent, and usually four (4%) percent and even much less of rosin acids.

Typical examples of recovered mixed fatty acids from tall oil useful in preparing the soaps for the water-soluble alkaline compositions of the invention are, with their percentage being by weight:

A. Oleic acid 47 Linoleic acid 40 Linolenic acid 5 Saturated fatty acids 3 Rosin acids 4 Unsaponifiables 1 B. Oleic acid 53.7 Linoleic acid 41.3 Saturated fatty acids 1 Rosin acids 5 C. Linoleic acid 44.16 Oleic acid 48.29 Saturated fatty acids 3.55 Rosin acids 4.0

The preparation of the polyamine soaps of the recovered mixed fatty acids from tall oil, as included in the water-soluble alkaline compositions of the invention is illustrated by, but not restricted to, the following examples using the above Example C composition of the recovered mixed fatty acids from tall oil:

EXAMPLE 1 Ethylenediamine soap of the recovered fatty acids from tall 0il.--One hundred and fifty milliliters of Water were heated to between 150 and 160 F. in a 600 milliliter stainless steel beaker and fifty milliliters of technical ethylenediamine (having water, and 0.9 sp. gr.) were stirred in with a high speed mixer. While continuing the mixing, one hundred milliliters of the foregoing Example C composition of recovered mixed fatty acids from tall oil (sp. gr. 0.86) were added dropwise from a separatory funnel, at a rate such that the reaction mixture continued within the foregoing temperature range by the heat of reaction. After all of this required quantity of these mixed acids was added, the stirring was continued at very high speed for several minutes thereafter. The finished product was a liquid soap composition of the invention containing some free unreacted amine and about fifty-six percent of water.

EXAMPLE 2 The procedure of Example 1 was repeated in all respects except that 75 milliliters each of the technical ethylenediamine and of the recovered mixed fatty acids from tall oil were used in place of their respective corresponding quantities in Example 1. The finished product was a liquid soap composition of the invention containing some free unreacted amine and about fifty-seven percent of water.

EXAMPLE 3 The procedure of Example 1 was repeated in all respects except that 100 milliliters of ethylenediamine and 50 milliliters of the recovered tall oil mixed fatty acids were used in place of their respectively corresponding quantities in Example 1. The finished product of the invention was a liquid soap composition containing some free unreacted amine and about 58 percent of water.

EXAMPLE 4 The procedure of Example 1 was repeated in all respects except that the ethylenediamine was replaced by an equal volume of propylenediamine (sp. gr. 0.86). The finished product was a liquid soap composition containing some free unreacted amine and about fifty-three percent of water.

EXAMPLE 5 The procedure of Example 2 was repeated in all respects except that the ethylenediamine was replaced by an equal volume of propylenediamine (sp. gr. 0.86). The finished product was a liquid soap composition containing some free unreacted amine and about fifty-three percent of water.

EXAMPLE 6 The procedure of Example 3 was repeated in all respects except that the ethylenediamine was replaced by an equal volume of propylenediamine (sp. gr. 0.86). The finished product was a liquid soap composition containing some free unreacted amine and about fifty-three percent of water.

EXAMPLE 7 The procedure of Example 1 was repeated in all respects excepts that the technical ethylenediamine was replaced by the same volume of diethylenetriamine (sp. gr. 0.95). The finished product was a relatively soft solid soap composition containing some free unreacted amine and fiftytwo percent of water.

EXAMPLE 8 The procedure of Example 2 was repeated in all respects except that the technical ethylenetriamine was replaced by the same volume of diethylenetriamine (sp. gr. 0.95). The finished product was a liquid soap composition containing some free unreacted amine and about fiftytwo percent of water.

EXAMPLE 9 The procedure of Example 3 was repeated in all respects except that the technical ethylenediamine was replaced by the same volume of diethylenetriamine (sp. gr. 0.95). The finished product was a liquid soap composition containing some free unreacted amine and fiftytwo percent of water.

The ultrasonic wave cleaning baths of the invention are prepared by dissolving in water an amount of the finished soap composition of any of foregoing Examples 1 through 9 or of Example 11 below, or of any herein'below described modifications of any of them, or of any mixture of any of those products, sufiicient to produce a pH of from about nine to about eleven in the resulting (so diluted) aqueous alkaline cleaning baths of the invention.

Expressed otherwise, the ultrasonic cleaning baths of the invention should contain by weight from about two to about four ounces of finished soap composition of the various examples of such compositions, per gallon of (the dilute) aqueous alkaline cleaning bath.

In general, the alkalinity of such dilute cleaning bath is the result of its containing on the average a conc. ntration of about 0.025 molal equivalent of the specific polya-mine which was used in the preparation of the original water-soluble alkaline concentrated soap composition (containing unreacted free polyamine).

The ultrasonic wave cleaning method of the invention is illustrated by, but not restricted to, the following parts of Example 10, in each of which parts there were cleaned incrustation-soiled metal articles, specifically die castings of the zinc alloy designated as Zamak #3 alloy (containing 3.54.3% aluminum, 0.1% copper, less than 0.1% iron, 0.030.08% magnesium, less than 0.005% of each of cadmium, lead, and sulfur, and the balance zinc to make a total of All of these castings were of the same shape, three inches long and having one side a continuous series of V-shaped grooves each one-sixteenth inch deep, and spaced twenty grooves to the inch of length.

Each of the castings was buffed by means of a soft stitchless rotating buff until all of the grooves were packed with the tripoli buffing composition used (designated Formax T6, and containing between sixty and seventy percent of abrasive assentially tripoli, from western Missouri, and the balance of a binder consisting of bufiing compound waxes and greases and stearin to the extent of twenty to fifteen percent of the entire composition of the buffing compound). The buffed castings were set aside and left alone to age for at least five days being treated by the process of this invention.

EXAMPLE The ultrasonic cleaning method of the invention. Separate ultrasonic cleaning bath solutions were prepared by dissolving each of the water-soluble polyamine and soap oontining compositions of, for example, Examples 1 through 9 respectively in'its corresponding separate quantity of water to obtain from each its separate respective dilute cleaning bath containing its corresponding polyamine and soap composition (With its excess unreacted amine) dissolved therein in a concentration of three ounces (by weight) per gallon of dilute aqueous alkaline cleaning bath.

Five hundred milliliters each resulting (i.e. dilute) ultrasonic cleaning solution or bath was placed alone in its own respective tall, liter beaker. All of these separate solutions in those beakers were heated on a hot plate to 150 F. Then all of the beakers were transferred to a ten gallon tank containing water held at 150 F. by thermostatic control. Each beaker was mounted vertically in the Water and with its open top extending above the water level and with the top surface of the cleaning baths in them below the level of the water in the tank.

The bottoms of the beakers extended to one inch above a pair of barium titanate transducers (sold by the Branson Ultrasonic Corporation). A 40 kilocycle per second electrical current was applied to the electrodes on the sides of the barium titanate inside of the transducers, from an electronic oscillatory unit rated at a capacity of 125 watts.

Up to ten castings requiring thus incrusted buffing compound to be cleaned from their grooves were placed in each of the beakers containing the respective diiferent testing solutions. Each was given a treatment by the sound waves transmitted from the transducers through the water in the tank, through the glass beaker and so through the cleaning bath solution, at a frequency of 40 kilocycles per second with maximum intensity until the castings were completely (i.e. 100%) clean.

The minimum time for each cleaning bath to produce this extent of cleaning was noted separately respectively for each of them, and used as an index of the cleaning eificiency of the cleaning bath and of the alkaline polyamine soap plus free polyamine cleaning composition dissolved in it. Repeat runs were conducted for each of the solutions tested.

The following average results were obtained with the cleaning solutions prepared from the compositions of Examples 1 through 9:

Cleaning solution from Example N 0.-

Complete cleaning time in seconds 6 Sodium metasilicate often delustres the surface of certain metal articles that are cleaned with aqueous solutions of it so that its utility with them ordinarily is questionable and undesirable.

It has been found as part of the invention that a watersoluble metasilicate as sodium metasilicate can be included, without the just above-indicated limitations, in preparing any of the water-soluble alkaline compositions of the invention, in addition to, or to replace a minor part of, any of the aforesaid polyamines, so long as such metasilicate is present to a lesser extent than the polyamine in the composition and does not exceed about one ounce (by weight) per gallon of dilute aqueous cleaning bath to be prepared from the metasilicate-containing water-soluble composition.

In addition, such water-soluble metasilicate-containing composition by enabling using a respective dilute aqueous alkaline ultra-sonic cleaning bath prepared from it, and such bath when used by the method of the invention, clean metal or other rigid articles having butfing compound soil incrusted in crevices, recesses or grooves on them in less time than is required to clean them, under equivalent ultrasonic operating conditions, by using the corresponding dilute cleaning solution bath prepared from the same water-soluble alkaline starting composition without any metasilicate included in it, or without any of its polyamine replace-d by any metasilicate.

Likewise, such water-soluble metasilicate can be included, with similar results in reducing the cleaning time, in any of the com-positions which, when used without any such metasilicate and operated at a temperature in the lower part of the temperature range may require a cleaning time somewhat longer than is compatible with the transit schedule of the work in relation to the immediately preceding and following steps in a series of steps in handling the articles.

Thus, also part of the invention are those water-soluble (concentrate) alkaline compositions as well as the dilute aqueous, alkaline cleaning bath solutions prepared from said (concentrate) compositions, which include a small concentration of a water-soluble meta-silicate such as an alkali metal metasilicate and ammonium metasilicate.

Such metasilicate (concentrate) compositions are illustrated by, but not restricted to, each of Examples 1 through 9 with one quarter of the respective polyamine in each of them replaced by the corresponding weight of sodium metasilicate. Similarly, the dilute aqueous alkaline cleaning baths of the invention, as well as the method using them, likewise are non-restrictingly illustrated by handling each of the nine different metasilicate concentrates obtained as described in the preceding sentence respectively by the same dilution described in the first paragraph of Example 10 and then using these baths respectively separately by the procedure and operating conditions further described in that example. Such concentrates, for example, can include sodium metasilicate in an amount to provide one ounce of it (by weight) per gallon when three ounces of the concentrate are dissolved in water per gallon of resulting (dilute) aqueous alkaline cleaning bath.

Thus, any water-soluble metasilicate suitable for use in any particular operation herein can be included to the extent of, or to replace, from about one-tenth percent to about twenty-five (25%) percent of the polyamine in the preparation of any of the soaps of the recovered mixed fatty acids from tall oil in making any of the watersoluble (concentrate) alkaline compositions, and so to be included in the corresponding dilute aqueous alkaline cleaning baths.

In the various Examples 1 through 9 and 10, suitable modifications and substitutions can be made within the scope of the invention. Thus, in some of the examples the polyamine soap may be replaced, or accompanied, in minor part by an alkali metal soap of the same recovered mixed tall oil acids of the corresponding example, such as a-sodium or potassium soap produced With them. To illustrate, the 285 grams of the mixed fatty acids of the following Example 11 may be added as there described to a solution of a single one or more or all of suitable Water-soluble alkali metal salts, for example, trisodium phosphate, sodium tetraborate-9H O (common borax), anhydrous sodium carbonate, or sodium metasilicate, dissolved in the water and their respective quantities and also under the conditions as therein given; and the hexylene glycol then dissolved in it and followed by solution of the ethylenediamine thereof in it. Alternatively, another embodiment of water-soluble alkaline soap composition of the invention is illustrated by, but not restricted to, the following example:

EXAMPLE 11 Following the procedure used in Example 1, 395 milliliters of water are heated in a two liter beaker to about 150 F. and while stirring there are added to, and dissolved in, it 100 grams of technical ethylenediamine, and then also 27 grams of hexylene glycol. While continuing the stirring, 285 grams of the foregoing Example C composition of recovered mixed fatty acids from tall oil were added dropwise from a separatory funnel, at such a rate that the reaction mixture was held around 150 F. by the heat of reaction. Thereafter there was homogeneously dissolved in the resulting ethylenediamine soap (concentrate) composition (containing excess unreacted diamine), 124 grams of trisodium phosphate-1211 0, 80 grams of common borax, 80 grams of anhydrous sodium carbonate, and 9 grams of sodium metasilicate, and the stirring was continued at high speed for several minutes. The finished product, after discontinuing the stirring, was a water-soluble alkaline liquid soap (concentrate) composition containing free unreacted ethylenediamine.

An ultrasonic (dilute) alkaline soap composition cleaning bath containing three ounces per gallon of that final product of Example 11 produced complete cleaning of castings such as described in Example 10, by the method of that example, in 60 seconds.

Where desirable, suitable surface active agents and/ or dispersing agents, that are compatible with the other ingredients of any of the compositions covered by the invention can be included. The significant feature of the invention is the presence in the alkaline soap compositions, of a significant quantity of free unreacted polyamine.

While the invention has been explained in detail by describing certain specific embodiments of it, it is understood that various modifications and substitutions may be made in any of the specific embodiments within the scope of the appended claims which are intended also to cover equivalents of the specific embodiments.

What is claimed is:

1. A composition useful in the cleaning of soil from deformations in rigid articles, which composition is (a) Water-soluble, (b) alkaline, and (c) comprises as its essential constituents for said cleaning utility:

(i) at least one lower aliphatic straight chain polyamine member of the class consisting of ethylene diamine, propylene diamine, and diethylenetriamine;

(ii) a soap made from reacting the recovered mixed fatty acids from tall oil and at least one of said polyamines, with said mixed acids used in such ratio to the polyamine reactant to leave an excess of the latter to be the said polyamine constituent (i) and to the extent of less than a mole thereof per mole of said soap constituent and such that an aqueous solution having a pH from about 9 to about 11 results when said polyamine and soap composition is dissolved in water in an amount of from about two to about four ounces by weight per gallon of aqueous solution; and

(iii) an alkali metal metasilicate or ammonium metasilicate in such concentration to provide up to about one ounce thereof by weight per gallon in said aqueous solution resulting when said composition is dissolved in water within the aforesaid range of concentration;

said resulting aqueous solution enabling completely removing generally within about a few minutes, and in less time than is required when using said composition without said metasilicate, incrustations of buffing compounds from recesses as well as grooves of rigid articles, upon subjecting them immersed in said aqueous solution to the influence of waves of ultrasonic frequency of from about fifteen to about forty kilocycles per second.

2. A composition as claimed in claim 1, wherein the metasilicate is sodium metasilicate.

3. An aqueous cleaning bath solution which is alkaline and contains dissolved therein per gallon of said bath solution from about two to about four ounces by weight of an alkaline composition which comprises as its essential constituents for its below mentioned incrustations removal property:

(i) at least one lower aliphatic straight chain polyamine member of the class consisting of ethylene diamine, propylene diamine, and diethylenetriamine; and

(ii) a soap made from reacting the recovered mixed fatty acids from tall oil and at least one of said polyamines, with said mixed acids used in such ratio to the polyamine reactant to leave an excess of the latter to be the said polyamine constituent (i) and to the extent of less than a mole thereof per mole of said soap constituent; said cleaning bath having a pH of from about 9 to about 11 and being effective at a temperature from about ambient temperature to about F. to enable complete removal of buffing compound incrustations from recesses as well as grooves on rigid articles immersed in said bath to occur within an interval of a few minutes while subjecting them therein to the influence of ultrasonic waves of from about fifteen to about forty kilocycles per second.

4. The method of removing dirt and soil incrustations, including even those of bufiing compounds, from recesses as well as grooves on rigid articles, which method comprises submerging such articles in an aqueous alkaline bath solution containing dissolved therein from about two to about four ounces by weight per gallon of said bath solution of an alkaline water-soluble composition comprising as its essential cosntituents for said dirt and soil incrustations removal:

(i) at least one lower aliphatic straight chain polyamine member of the class consisting of ethylene diamine, propylene diamine, and diethylenetriamine; and

(ii) a soap made from reacting the recovered mixed fatty acids from tall oil and at least one of said polyamines, with said mixed acids used in such ratio to the polyamine reactant to leave an excess of the latter to be the said polyamine constituent (i) and to the extent of less than a mole thereof per mole of said soap constituent, whereby said bath solution has a pH from about 9 to about 11; and subjecting such so submerged articles to the influence of waves of ultrasonic frequency, of the order from about fifteen to about forty kilocycles per second, transmitted to the articles through said aqueous alkaline bath, and for a time within a few minutes sufficient completely to clean the incrustations from said articles.

5. An aqueous cleaning bat-h comprising in aqueous solution, as its essential ingredients for its below mentioned incrustation removal property, from about two to about four ounces by weight of an alkaline composition as claimed in claim 1 dissolved therein per gal- Ion of said bath; said cleaning bath having a pH of from about 9 to about 11 and being effective at a temperature from about ambient temperature to about 160 F. to en able complete removal of buffing compound incrustations from recesses as well as grooves on rigid articles submerged in said bath to occur within an interval of under a few minutes and less than is required when using said bath without said metasilicate, while subjecting them therein to the influence of ultrasonic waves of from about fifteen to about forty kilocycles per second.

6. The method of removing dirt and soil incrustations, including even those of bufling compounds, from recesses as well as grooves on rigid articles, which comprises submerging such articles an an aqueous alkaline bath containing dissolved in its water per gallon, as its essential agents for the aforesaid incrustation removal activity, from about two to about four ounces by weight of an alkaline water-soluble composition as claimed in claim 1; and subjecting such so submerged articles to the influence of waves of ultrasonic frequency, of the order from about fifteen to about forty kilocycles per second, transmitted to the articles through said aqueous alkaline cleaning bath, and for a time within a few minutes suflicient completely to clean the incrustations from said articles.

7. A liquid aqueous alkaline soap-containing composition comprising, as its essential ingredients for its below mentioned incrustation removal property, (i) the soap formed by reacting in sufficient water about one hundred parts of ethylenediamine and about 285 parts of the recovered mixed fatty acids of tall oil, and (ii) homogeneously dissolved therewith in the water about 124 parts of trisodium phosphate-EH 0, about 80 parts of ordinary borax, about 80 parts of anhydrous sodium carbonate, and about 9 parts of sodium metasilicate; all of the aforesaid parts being by weight the dilute aqueous alkaline bath solution resulting when said soap-containing composition is dissolved in water to a concentration of from about two to about four ounces thereof by weight, exclusive of the water used as reaction medium, per gallon of resulting dilute aqueous solution, being effective at a temperature from about ambient temper ature to about 160 F. to enable complete removal of buffing compound incrustations from recesses and grooves on rigid articles while subjecting said articles submerged in said bath solution to the influence of ultrasonic waves of from about fifteen to about forty kilocycles, to occur in less time than such complete removal can occur when sodium metasilicate is omitted.

8. An aqueous cleaning bath comprising in aqueous solution, as its essential agents for its below mentioned incrustation removal activity, per gal-Ion of bath solution the alkaline soap composition of claim 7 to the extent of about two to about four ounces by weight of the content thereof exclusive of the water used as reaction medium; said cleaning bath having a pH of from about 9 to about 11 and being effective at a temperature from about ambient temperature to about 160 F. to enable complete removal of buffing compound incrustations from recesses as well as grooves on rigid articles to occur under the influence of ultrasonic waves of from about fifteen to about forty kilocycles per second, and within an interval of under a few minutes.

9. The method of removing dirt and soil incrustations,

including even those of buffing compounds, from recesses as well as grooves on rigid articles, which comprises submerging such articles in an aqueous alkaline bath as claimed in claim 8, and subjecting the articles so submerged to the influence of waves of ultrasonic frequency, of the order from about fifteen to about forty kilocycles per second, transmitted to the articles through the aqueous alkaline cleaning bath, and for a time within a few minutes sufficient completely to clean the incrustations from said articles.

10. An aqueous alkaline liquid soap containing composition "as claimed in claim 7, wherein there also is dissolved in said water about 27 parts of hexyleneglycol.

11. An aqueous cleaning bath comprising in aqueous solution, as its essential agents for its aforesaid incrustation removal activity, per gallon of bath solution the alkaline soap containing composition of claim 10 to the extent of about two to about four ounces by weight of the content thereof exclusive of the water used as reaction medium; said cleaning bath having a pH of from about 9 to about 11 and being effective at a temperature from about ambient temperature to about F. to enable complete removal of buffing compound incrustations from recesses as well as grooves on rigid articles submerged in said bath to occur within an interval of under a few minutes while subjecting them therein to the influence of ultrasonic waves of from about fifteen to about forty kilocycles per second.

12. The method of removing dirt and soil incrustations, including even those of buffing compounds, from recesses as Well as grooves on rigid articles, which comprises submerging such articles in an aqueous alkaline bath as claimed in claim 11, and subjecting such so submerged articles to the influence of waves of ultrasonic frequency, of the order from about fifteen to about forty kilocycles per second, transmitted to the articles through said aqueous alkaline cleaning bath, and for a time within a few minutes sufficient completely to clean said articles.

Hexylene Glycol, publ. of Shell Chemical Corp., Technical Booklet SCzSO-l (1950) 28 pp., pp. 8, 18 and 19 relied upon.

LEON D. ROSDOL, Primary Examiner.

ALBERT T. MEYERS, JULIUS GREENWALD,

Examiners.

S. H. BLECH, M. WEINBLATI, Assistant Examiners. 

4. THE METHOD OF REMOVING DIRT AND SOIL INCRUSTATIONS, INCLUDING EVEN THOSE OF BUFFING COMPOUNDS, FROM RECESSES AS WELL AS GROOVES ON RIGID ARTICLES, WHICH METHOD COMPRISES SUBMERGING SUCH ARTICLES IN AN AQUEOUS ALKALINE BATH SOLUTION CONTAINING DISSOLVED THEREIN FROM ABOUT TWO TO ABOUT FOUR OUNCES BY WEIGHT PER GALLON OF SAID BATH SOLUTION OF AN ALKALINE WATER-SOLUBLE COMPOSITION COMPRISING AS ITS ESSENTIAL CONSTITUENTS FOR SAID DIRT AND SOIL INCRUSTATIONS REMOVAL: (I) AT LEAST ONE LOWER ALIPHATIC STRAIGHT CHAIN POLYAMINE MEMBER OF THE CLASS CONSISTING OF ETHYLENE DIAMINE, PROPYLENE DIAMINE, AND DIETHYLENETRIAMINE; AND (II) A SOAP MADE FROM REACTING THE RECOVERED MIXED FATTY ACIDS FROM TALL OIL AND AT LEAST ONE OF SAID POLYAMINES, WITH SAID MIXED ACIDS USED IN SUCH RATIO TO THE POLYAMINE REACTANT TO LEAVE AN EXCESS OF THE LATTER TO BE THE SAID POLYAMINE CONSTITUENT (I) AND TO THE EXTENT OF LESS THAN A MOLE THEREOF PER MOLE OF SAID SOAP CONSTITUENT, WHEREBY AID BATH SOLUTION HAS A PHY FROM ABOUT 9 TO ABOUT 11; AND SUBJECTING SUCH SO SUBMERGED ARTICLES TO THE INFLUENCE OF WAVES OF ULTRASONIC FREQUENCY, OF THE ORDER FROM ABOUT FIFTEEN TO ABOUT FORTY KILOCYCLES PER SECOND, TRANSMITTED TO THE ARTICLES THROUGH SAID AQUEOUS ALKALINE BATH, AND FOR A TIME WITHIN A FEW MINUTES SUFFICIENT COMPLETELY TO CLEAN THE INCRUSTATIONS FROM SAID ARTICLES. 